CN101255223B - Terpolymer rubber having low rolling resistance and high wet-sliding resistant performance, preparation and uses thereof - Google Patents
Terpolymer rubber having low rolling resistance and high wet-sliding resistant performance, preparation and uses thereof Download PDFInfo
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- CN101255223B CN101255223B CN2007100641123A CN200710064112A CN101255223B CN 101255223 B CN101255223 B CN 101255223B CN 2007100641123 A CN2007100641123 A CN 2007100641123A CN 200710064112 A CN200710064112 A CN 200710064112A CN 101255223 B CN101255223 B CN 101255223B
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Abstract
The invention relates to a terpolymer of mono-ethylene arene, conjugated diene 1 and conjugated diene 2, preparation method thereof and application thereof. The obtained copolymer rubber has good anti-wet slipping performance and low rolling resistance. The terpolymer has greatly low rolling resistance and fine anti-wet slipping performance and the tan Delta is below 0.071 at 60 degree and the tan Delta is above 0.523 at 0 degree, wherein the ratio of the tan Delta at 0 degree to the tan Delta at 60 degree is above 7. The invention can be widely used in rubber articles field such as tyre.
Description
Invention field
The present invention relates to a kind of terpolymer rubber, in particular to terpolymer of a kind of conjugated diene 1, conjugated diene 2 and monovinylarene and preparation method thereof.Terpolymer rubber of the present invention has low-rolling-resistance and good wet-sliding resistant performance, can be widely used in as rubber item fields such as tires.
Background technology
At the rubber various commonly used that uses at present, as cis-1,4-polybutadiene rubber (BR), natural rubber (NR), emulsion polymerized styrene butadiene rubber (ESBR), solution polymerization styrene-butadiene rubber (SSBR) etc., they have own special advantages, but also deficiency are arranged.Flexible best as BR, rolling resistance is little, but wet-sliding resistant performance is relatively poor.And NR is flexible placed in the middle, the rolling resistance better performances, but wet-sliding resistant performance is general.The higher SBR wet-sliding resistant performance of styrene-butadiene rubber(SBR) (SBR), especially styrene content is superior, but the rolling resistance performance is relatively poor.As seen in various conventional rubbers, any all various performance demands of balance preferably.From present data, the wet-sliding resistant performance of rubber generally characterizes indirectly with rubber tan δ value during in 0 ℃ in dynamic properties test, and common this value more than 0.24 all is being wet-sliding resistant performance sample preferably; And the rolling resistance performance is generally represented with the tan δ value of rubber 60 ℃ the time, and this value all is being the sample of rolling resistance better performances below 0.12 usually.Simultaneously for tyre rubber (second-order transition temperature is below-30 ℃), the ratio of the tan δ value when the tan δ value in the time of its 0 ℃ and 60 ℃ is high more, and its safety performance and thermogenesis performance are good more.
In recent years, along with the raising of people's awareness of saving energy with to the further concern of tire safe capability, also progressively improving, especially require automobile that wet-sliding resistant performance and lower rolling resistance performance are preferably arranged to the requirement of tire.And in order to obtain more satisfactory low-rolling-resistance performance, in the reaction of adopting anionoid polymerization synthetic rubber product, adopting lithium alkylide mostly is initiator, contains tin compound (as tin tetrachloride) in the adding of the later stage of building-up reactions and carries out coupling.This method can reduce rolling resistance preferably, but the link coupled method can not guarantee on each macromolecular chain segment of polymkeric substance tin atom is arranged all.In order to address this problem, research and propose and in initiator, introduce tin atom, as United States Patent (USP) 5,502,129 just to adopt the tributyl tin lithium be that initiator synthesizes SSBR, the rolling resistance performance of finding resulting polymers after tested is outstanding, shows that sample tests through dynamic properties, and the tan δ value in the time of its 65 ℃ is 0.0938.And adopt n-Butyl Lithium to cause, be 0.1073 with the tan δ value of the end capped product of tributyl tin chlorine 65 ℃ the time.As seen adopt in the rubber product of introducing the initiator initiation preparation that contains tin atom therein, can reduce the rolling resistance performance better.
Simultaneously, for the over-all properties of balance rubber preferably, Nordsiek has proposed the notion of integrated rubber (referring to K H Nordsiek, The " integral rubber " concept-anapproach to an ideal tire tread rubber, Kautschuk, Gummi Kunststoffe, 1985,38 (3): 178-185), this rubber is the over-all properties of balance rubber better.United States Patent (USP) 4,843,120 have reported the integrated rubber of the synthetic many second-order transition temperatures of two-step approach that adopt two reactor successive polymerizations, wherein in first still, add styrene monomer, isoprene monomer, divinylic monomer, n-butyl lithium initiator, inert organic solvents, polar additive in 85 ℃ of following polyase 13s 0 minute, and after transformation efficiency reaches 60%, reaction mixture is transferred in second still, further reacts down and reached 100% transformation efficiency in 1 hour in 88 ℃ to 91 ℃.Products therefrom has a plurality of second-order transition temperatures, and the tan δ value in the time of its 60 ℃ is 0.091.As seen integrated rubber is in the distinctive feature that oneself is arranged aspect the reduction rolling resistance.
Even so, along with rubber industry, the especially development of tire industry, the tyre rubber material is had higher requirement, hope can be found has the excellent more low-rolling-resistance and the elastomeric material of high wet-sliding resistant performance.
Summary of the invention
Situation in view of above-mentioned prior art, the present inventor has carried out extensive studies in the anionic copolymerization field of conjugated diene and monovinylarene, unexpectedly find, by adopting stanniferous single two kinds of different conjugated dienes of lithium initiator initiation and monovinylarene to carry out terpolymer, add ethers simultaneously, conditioning agents such as amine are regulated, and optional add coupling agent such as the many chlorine compounds of stanniferous carry out coupling, can obtain to have the copolymer product of extremely low rolling resistance performance and good wet-sliding resistant performance, tan δ value in the time of its 60 ℃ is below 0.071,0 ℃ tan δ value is more than 0.523, and the ratio of the tan δ value when the tan δ value its 0 ℃ time the and 60 ℃ is more than 7.
Therefore, an object of the present invention is to provide the terpolymer of a kind of conjugated diene 1, conjugated diene 2 and monovinylarene, this multipolymer has good low-rolling-resistance performance, have excellent wet-sliding resistant performance and more satisfactory comprehensive physical and mechanical properties simultaneously, very suitable preparation high-performance tire uses.
Another object of the present invention provides a kind of method for preparing above-mentioned terpolymer.
A further object of the present invention provides the application of above-mentioned terpolymer in the preparation high-performance tire.
Need to prove that term " terpolymer " and " terpolymer rubber " can exchange use in the present invention.
Particularly, the invention provides a kind of novel terpolymer, it is formed through terpolymer by conjugated diene 1, conjugated diene 2 and monovinylarene, it is characterized in that all containing a tin atom at the head end of each bar polymer segment of this terpolymer.
In terpolymer of the present invention, the number-average molecular weight of described multipolymer is 1.0 * 10
5-5.0 * 10
5, preferred 1.2 * 10
5-2.5 * 10
5Molecular weight distribution is 1.1-2.5, and preferred molecular weight distributes and is not less than 1.2.
In a preferred embodiment of the invention, described terpolymer can be chosen wantonly by coupling, and coupling efficiency is 20%-100%, preferred 30%-80%.
In terpolymer of the present invention, described conjugated diene 1 and conjugated diene 2 are different, and they are meant any monomer that has conjugated double bond in its molecule, and the example includes but not limited to C
4-C
6Conjugated diene monomer is as divinyl, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethylbutadiene and composition thereof.Described conjugated diene 1 and conjugated diene 2 are preferably divinyl and isoprene.
In terpolymer of the present invention, described mono vinyl arenes monomer is meant the aromatic monomer that has a vinyl substituted base on its aromatic ring, the example includes but not limited to the vinylbenzene that vinylbenzene or alkyl replace, as vinylbenzene, Vinyl toluene, alpha-methyl styrene, 4-t-butyl styrene, 4-vinyl toluene, 3,5-diethylbenzene ethene, 3,5-di-n-butyl vinylbenzene, 4-n-propylbenzene ethene, 4-dodecyl vinylbenzene and composition thereof; Optimization styrene, Vinyl toluene, α-vinyl toluene and composition thereof; Vinylbenzene most preferably.
In terpolymer of the present invention, be benchmark in the weight of terpolymer, the content of described mono vinyl arenes monomer is 10-40 weight %, is preferably 15-25 weight %; Conjugated diene 1 monomeric content is 5-85 weight %, is preferably 20-60 weight %; Conjugated diene 2 monomeric content are 5-85 weight %, are preferably 20-60 weight %.
In embodiments of the invention, preferably use vinylbenzene (St), isoprene (Ip) and three kinds of monomers of divinyl (Bd) as comonomer, wherein the content of St is 10-40 weight %, is preferably 15-25 weight %; The content of Ip is 5-85 weight %, is preferably 20-60 weight %; The content of Bd is 5-85 weight %, is preferably 20-60 weight %.Because optional coupling, making has the part coupled product to be present in the polymkeric substance.Therefore, the main component in the gained multipolymer is R
1-Sn-St-Ip-Bd and (R
1-Sn-St-Ip-Bd)
nTwo kinds of structures of-Sn (n is 1-4) (R wherein
1From initiator residue).Three kinds of monomers of St, Ip and Bd can exist in random mode in multipolymer, can also have long polybutadiene block or polyisoprene blocks.The microtexture of gained terpolymer is: 1, and the 2-Bd structural content is 5-65 weight %, is preferably 10-30 weight %; 3, the 4-Ip structural content is 5-65 weight %, is preferably 10-30 weight %.
Conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer of the present invention has following constitutional features:
1) head end of each bar polymer segment of terpolymer all contains a tin atom.
2) content of mono vinyl arenes monomer is 10-40 weight %, is preferably 15-25 weight %.
3) conjugated diene 1 monomeric content is 5-85 weight %, is preferably 20-60 weight %.
4) conjugated diene 2 monomeric content are 5-85 weight %, are preferably 20-60 weight %.
5) number-average molecular weight of terpolymer is 1.0 * 10
5-5.0 * 10
5, preferred 1.2 * 10
5-2.5 * 10
5Molecular weight distribution is 1.1-2.5, preferably is not less than 1.2.
6) through after the optional coupling, the coupling efficiency of terpolymer is 20-100%, is preferably 30-80%.
The invention also discloses the preparation method of above-mentioned terpolymer, it is included in and adopts stanniferous single lithium compound in the inert gas environment is initiator, in one or more varsols in the presence of polar additive, carry out the random copolymerization of conjugated diene 1/ conjugated diene 2/ mono vinyl arenes monomer, after polymerization is finished, add terminator and stop living polymer chains.
Particularly, the following stanniferous single lithium compound that has independent intellectual property right of preferred use is as initiator (Granted publication CN1181101C) in the preparation method of terpolymer of the present invention, and the full content of this patent is incorporated herein for reference.Described stanniferous single lithium compound can be represented with following general formula (1):
R
3SnY
aZY
bLi (1)
Wherein: R is C
1-C
20Alkyl, C
3-C
20Cycloalkyl or C
6-C
20Aryl or substituted aryl; Z is straight chain or branched C
1-C
20Bivalent hydrocarbon radical, C
6-C
30Arylidene or replacement arylidene; Y is a conjugated diolefine homopolymerization group, monovinylarene homopolymerization group or conjugated diolefine and monovinylarene copolymerization group; A is 0-6,0＜a+b≤6, and during b=0, a must equal 0.
Preferred stanniferous single lithium compound that the present invention uses is a=0 and b=0, available following general formula (1a) expression:
R
3SnZLi (1a)。
Another kind of preferred stanniferous single lithium compound that the present invention uses is a=0 and b ≠ 0, available following general formula (1b) expression:
R
3SnZY
bLi (1b)。
The preferred stanniferous single lithium compound of the class again that the present invention uses is a ≠ 0 and b ≠ 0, available following general formula (1c) expression:
R
3SnY
aZY
bLi (1c)。
In another aspect of this invention, described terpolymer also can prepare by using conventional initiator tributyl tin lithium.
In the preparation method of conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer of the present invention, operable rare gas element is the gas used always as nitrogen, argon gas, helium etc.
In the preparation method of conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer of the present invention, the solvent of use can be an anionoid polymerization field varsol commonly used.Described varsol can comprise as the naphthenic hydrocarbon that contains 5-7 carbon atom, aromatic hydrocarbons, isoparaffin or its mixture.Specific examples is the varsol that is selected from benzene, toluene, hexane, hexanaphthene, pentane, heptane, hexane/hexanaphthene mixture.Wherein these solvents can use separately or mix use with two or more.The consumption of preferred control solvent so that monomer concentration at 5-30 weight %, be preferably in the scope of 8-20 weight %.
In the preparation method of conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer of the present invention, can use polar additive as irregular agent and structure regulator.Used polar additive is the conventional reagent in the synthetic field of rubber, comprise containing oxygen, nitrogenous, sulfur-bearing or phosphorated compound or their mixture, its specific examples includes but not limited to ether, dibutyl ether, tetrahydrofuran (THF), glycol dimethyl ether, diglyme, dioxane, crown ether, triethylamine, Tetramethyl Ethylene Diamine, HMPA, potassium tert.-butoxide, tertiary amyl alcohol potassium, potassium lauryl, alkyl benzene sulphonate (ABS) potassium, sodium alkyl benzene sulfonate and composition thereof.Consumption to polar additive has no particular limits in preparation method of the present invention, and the consumption of preferred polar additive is recently weighed with the mole of polar additive and stanniferous single lithium compound.The mol ratio of general polar additive and stanniferous single lithium compound is 0.1-200, is preferably 1.0-100.
In the preparation method of conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer of the present invention, after polyreaction is finished, can stop living polymer chains by anionoid polymerization field mode commonly used.Used terminator is commonly used those in anionoid polymerization field, and for example water or alcohol are as methyl alcohol, ethanol, n-propyl alcohol, Virahol etc.
In the preparation method of conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer of the present invention, after polyreaction was finished, before terminator added, the optional coupling agent that can add carried out coupling to the multipolymer that generates.The consumption of coupling agent will guarantee the segment of 20-100% by coupling, and preferred coupling efficiency is 30-80%.Operable coupling agent includes but not limited to many vinyl aromatic (co)s hydro carbons, polyfunctional epoxies, imines class, aldehydes, ketone, acid anhydride class, ester class, isocyanates and polyhalogenide etc.After coupling, can directly add the terminator termination reaction, perhaps after coupling, can add sn-containing compound part or all of end-blocking is partly carried out in coupling not, carry out the termination reaction operation behind the end-blocking again.Used end-capping reagent is the conventional end-capping reagent in the synthetic field of rubber, and as trialkyltin chlorine, wherein alkyl contains 1-8 carbon atom, as tin trimethyl chlorine, triethyltin chlorine, tributyl tin chlorine.The mol ratio of the same not coupling part of end-capping reagent is 0.2-1.0, is preferably 0.5-1.0.
In the preparation method of conjugated diene 1/ conjugated diene 2/ monovinylarene terpolymer of the present invention, the temperature and pressure of polyreaction there is not special requirement.The general polymerization temperature is controlled between 10 ℃ to 200 ℃, preferably between 45 ℃ to 150 ℃, pressure at 0.05MPa between the 0.5MPa, preferably at 0.1MPa between the 0.3MPa.Reaction times is between 1.5 hours to 3 hours.
Randomly, can further handle, for example before drying treatment, anti-aging agent be added in the glue terpolymer composition glue liquid of the present invention.Operable anti-aging agent comprises Irganox1520 (Switzerland vapour Bagong department) according to the present invention, four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (promptly 1010)/tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester (promptly 168)) compound anti-aging agent (wherein 168 content is not higher than 50 weight %), 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl (promptly 1076)/tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester (promptly 168) compound anti-aging agent (wherein 168 content is not higher than 50 weight %).After adding anti-aging agent such as Irganox1520 and be two keys of preventing in the conjugated diene polymer molecular chain and oxygen etc. and contacting under certain condition, produce adverse consequences down such as heat effect, as reactions such as crosslinked, degradeds, increase the gel content of rubber in toluene solution.According to the present invention, the consumption of anti-aging agent is 0.005-0.5 weight % based on dried glue weight.At last, the polymkeric substance glue can precipitate from solvent by similar fashion such as alcoholization precipitation, centrifugation, filtration, decant, hot water cohesions separates out, and also can adopt the stripping mode that the volatile organic solvent in the multipolymer is separated.
Terpolymer rubber by synthetic method preparation of the present invention can be used to prepare various rubber items, especially is fit to make tire and uses.
Terpolymer rubber of the present invention is compared with copolymer rubber commonly used at present owing to as described below, has splendid wet-sliding resistant performance and excellent low-rolling-resistance performance:
(1) owing to use stanniferous single lithium compound to be initiator, make the head end of each bar polymer segment of synthetic terpolymer all contain a tin atom, can reduce the rolling resistance of copolymer rubber effectively.
(2) most of polymer segment is carried out coupling, reduced the quantity of polymer free terminal, can effectively improve the rolling resistance performance of copolymer rubber.
(3) adopt again at the end of link coupled polymkeric substance not and contain tin reagent and carry out end-blocking, further introduced tin atom, can further reduce the rolling resistance of copolymer rubber.
(4) in copolymer rubber, contain two kinds of conjugated dienes, especially contain the conjugated diene of side group structure, can improve the wet-sliding resistant performance of copolymer rubber.
(5) the tan δ value of terpolymer rubber of the present invention in the time of 60 ℃ is below 0.071, and the tan δ value in the time of 0 ℃ is more than 0.523, and the ratio of the tan δ value when the tan δ value its 0 ℃ time the and 60 ℃ is more than 7.
Embodiment
Below in conjunction with embodiment and Comparative Examples the present invention is further specified, but be not intended to limit protection scope of the present invention.
Testing method:
1, the microtexture of synthetic terpolymer rubber adopts U.S. Nicolet company 560 type fourier transform infrared spectroscopies to measure, and solvent is CS2.
2, molecular weight, molecular weight distribution and coupling efficiency adopt the U.S. 150C of WATERS company type gel permeation chromatograph (GPC) to measure, and THF is a moving phase, and narrow distribution polystyrene is a standard specimen, and temperature is 25 ℃.
3, second-order transition temperature adopts the U.S. MDSC2910 of TA company type dsc (DSC) instrument to measure, and be 60 seconds modulation period, modulated amplitude ± 1.5 ℃, 10 ℃/min of temperature rise rate, nitrogen protection, flow velocity 50mL/min.
4, dynamic properties adopts the U.S. DMA-2980 of TA company type viscoelastic spectrometer to measure, frequency 2Hz, and 5 ℃/min of temperature rise rate, temperature-120 ℃ is to 100 ℃, sample size 40mm * 5mm * 1mm.
5, rubber adopts mill mixing, the roller temperature be carry out under 50 ± 5 ℃ mixing, mixing after, park after 4 hours and carry out back mixing, back mixing finishes, and parks half an hour.With the vulcanizing press sulfuration, cure conditions: 145 ℃ of temperature, more than the pressure 10MPa, sulfuration 35min cools off film then from mould, be used for performance test.
6, vulcanizating glue physical performance adopts XLL250 type rubber puller system to press GB/T528-1998 mensuration; Mooney viscosity adopts Japanese SHIMADZU mooney viscosity instrument to measure by GB/T1232-92.
Embodiment 1The preparation of tributyl tin lithium initiator
With the 100ml three-necked bottle pump drainage several and the applying argon gas of induction stirring are housed, add the diethyl ether solution that 40ml is dissolved with lithium sand then, drip 15ml (C
4H
9)
3SnCl, wherein metallic lithium and (C
4H
9)
3The mol ratio of SnCl is 2:1.Stopped reaction after reacting 3 to 4 hours under 5 ℃ to 10 ℃.Obtain clarifying blackish green solution after filtering.Measure active lithium concentration and preservation by two volumetrys (referring to Gilman and K.F. Cartlidge, J.Organomet.Chem., 1994,2447).
Embodiment 2(C
4H
9)
3Sn (CH
2)
4The preparation of Li initiator
With the 100ml three-necked bottle pump drainage several and the applying argon gas of induction stirring are housed, add the two-lithium compound Li (CH that 20ml prepares then
2)
4The diethyl ether solution of Li (1.996M) drips (C
4H
9)
3The 15ml THF solution of SnCI, wherein two-lithium compound Li (CH
2)
4Li and (C
4H
9)
3The mol ratio of SnCl is 1:1.Stopped reaction after reacting 2 hours under 10 ℃.Obtain clarifying yellow solution after filtering.By two titration measuring active lithium concentration and preservation.
Embodiment 3-5(C
4H
9)
3SnZY
bThe preparation of Li initiator
With the 250ml three-necked bottle pump drainage several and the applying argon gas of induction stirring are housed, add the two-lithium compound LiZLi for preparing then, drip (the C of equimolar amount
4H
9)
3The 5ml THF solution of SnCI, 10 ℃ are reacted stopped reaction after 2 hours down, add the divinyl and the solvent that measure, and 20 ℃ are reacted stopped reaction after 1 hour down, measure active lithium concentration and also preserve.Testing data is listed in the table 1.
Embodiment 6
In 5 liters of stainless steel stirring tanks, add 3300 milliliters of hexanaphthenes, 70 gram vinylbenzene, 140 gram divinyl, 140 gram isoprene, 17 milliliters of tetrahydrofuran solutions, and at 55 ℃ of 8 milliliters of stanniferous single lithium compound initiators (solvent is a hexanaphthene) that add preparation among the embodiment 4 down, reacted 60 minutes, the system top temperature reaches 85 ℃.Add 5 milliliters of SnCl then
4Solution continues reaction, adds 6 milliliters of aqueous isopropanol terminators in 90 minutes.Add anti-aging agent Irganox1520 in the glue that obtains, add-on is 0.2 weight % of dried glue, with hot water cohesion, hot-rolling drying treatment.Sample is carried out the physicals test.The result is as shown in table 2.
The microtexture that obtains this synthetic terpolymer rubber by above-mentioned determination of infrared spectroscopy is: 1, and 2-Bd% (mass ratio) 13.72%, 1,4-Bd% (mass ratio) is 26.28%, 1, and 4-Ip% (mass ratio) is 23.6%, 3,4-Ip% (mass ratio) is 16.4%.
In addition, adopt the method identical with embodiment 6 to compare the terpolymer of vinylbenzene, divinyl and the isoprene of example 1, difference is to use n-Butyl Lithium as initiator.The result is as shown in table 2.
Need to prove that below the Comparative Examples of Chu Xianing is and uses n-Butyl Lithium to replace corresponding stanniferous single lithium compound as initiator, the condition that is adopted among other condition and the corresponding embodiment is identical.
Table 2
| Project | Embodiment 6 | Comparative Examples 1 | SSBR (1) | SSBR 2305 (2) | ESBR 1500 (2) | NR (2) |
| M Peak value(×10 5) | 17.6 | 21.6 | 12.0 | ? | ? | ? |
| Coupling (%) | 47.0 | 42.0 | 56.0 | ? | ? | ? |
| Shore hardness | 64 | 66 | 60 | 65 | 65 | 66 |
| Tear strength (MPa) | 39 | 40 | 41 | 38 | 32 | 30 |
| Tension set (%) | 5 | 9 | 8 | 10 | 13 | 6 |
| Mooney viscosity | 83 | 71 | 62 | 56 | 55 | 86 |
| 300% tensile modulus (MPa) | 11.9 | 10.5 | 11.2 | 13.0 | 10.4 | 12.4 |
| Tensile strength at yield (MPa) | 21.8 | 20.6 | 23.0 | 24.0 | 22.9 | 25.0 |
| Specific elongation (%) | 456 | 484 | 490.0 | 499 | 528 | 484 |
| Tg(℃) | -40 | -47 | -45 | -42.2 | -40.4 | -66.2 |
| tanδ(0℃) | 0.5238 | 0.3628 | 0.3545 | 0.2359 | 0.2020 | 0.1078 |
| tanδ(60℃) | 0.0704 | 0.0952 | 0.0700 | 0.1091 | 0.1128 | 0.0932 |
| Tan δ ratio (0 ℃/60 ℃) | 7.44 | 3.81 | 5.06 | 2.16 | 1.79 | 1.16 |
Annotate: (1) adopt with embodiment in the SSBR for preparing of used identical initiator;
(2) SSBR2305, ESBR1500 and NR are all the product that is commercially available.
Embodiment 7
In 5 liters of stainless steel stirring tanks, add 3300 milliliters of hexanaphthenes, 70 gram vinylbenzene, 145 gram divinyl, 135 gram isoprene, 1.0 milliliters of Tetramethyl Ethylene Diamine solution, and at 55 ℃ of 6 milliliters of stanniferous single lithium compound initiators (solvent is a hexanaphthene) that add embodiment 2 preparations down, reacted 120 minutes, the system top temperature reaches 80 ℃.Add 5 milliliters of SnCl then
4Solution continues reaction, 6 milliliters of aqueous isopropanol terminators in 150 minutes.Add anti-aging agent Irganox1520 in the glue that obtains, add-on is 0.2 weight % of dried glue, with hot water cohesion, hot-rolling drying treatment.Sample is carried out the physicals test, and the result is as shown in table 3 below.
The microtexture that obtains this synthetic terpolymer rubber by above-mentioned determination of infrared spectroscopy is: 1, and 2-Bd% (mass ratio) 14.57%, 1,4-Bd% (mass ratio) is 26.86%, 1, and 4-Ip% (mass ratio) is 21.21%, 3,4-Ip% (mass ratio) is 17.36%.
Table 3
| Project | Embodiment 7 | Comparative Examples 2 |
| M Peak value(×10 5) | 14.7 | 14.5 |
| Coupling (%) | 61 | 66 |
| Shore hardness | 66 | 66 |
| Tear strength (MPa) | 39 | 43 |
| Tension set (%) | 10 | 11 |
| Mooney viscosity | 82 | 51 |
| 300% tensile modulus (MPa) | 12.3 | 11.2 |
| Tensile strength at yield (MPa) | 25.6 | 21.8 |
| Specific elongation (%) | 509 | 505 |
| Tg(℃) | -37.1 | -39.6 |
| tanδ(0℃) | 0.5505 | 0.4906 |
| tanδ(60℃) | 0.0692 | 0.0918 |
| Tan δ ratio (0 ℃/60 ℃) | 7.96 | 5.34 |
Embodiment 8
In 5 liters of stainless steel stirring tanks, add 3300 milliliters of hexanaphthenes, 80 gram vinylbenzene, 120 gram divinyl, 150 gram isoprene, 17 milliliters of tetrahydrofuran solutions, and at 55 ℃ of 14 milliliters of stanniferous single lithium compound initiators (solvent is a hexanaphthene) that add embodiment 3 preparations down, reacted 80 minutes, the system top temperature reaches 83 ℃.Add 5 milliliters of SiCl then
4Solution continues reaction, adds 6 milliliters of aqueous isopropanol terminators in 110 minutes.Add anti-aging agent Irganox1520 in the glue that obtains, add-on is 0.2 weight % of dried glue, with hot water cohesion, hot-rolling drying treatment.Sample is carried out the physicals test, and the result is as shown in table 4 below.
The microtexture that obtains this synthetic terpolymer rubber by above-mentioned determination of infrared spectroscopy is: 1, and 2-Bd% (mass ratio) 12.03%, 1,4-Bd% (mass ratio) is 22.25%, 1, and 4-Ip% (mass ratio) is 24.86%, 3,4-Ip% (mass ratio) is 18.06%.
Table 4
| Project | Embodiment 8 | Comparative Examples 3 |
| M Peak value(×10 5) | 21.9 | 21.2 |
| Coupling (%) | 49 | 48 |
| Shore hardness | 66 | 66 |
| Tear strength (KN/m) | 39 | 41 |
| Tension set (%) | 7 | 9 |
| Mooney viscosity | 76 | 63 |
| 300% tensile modulus (MPa) | 12.1 | 11.3 |
| Tensile strength at yield (MPa) | 23.5 | 20.2 |
| Specific elongation (%) | 496 | 470 |
| Tg(℃) | -36.5 | -42.9 |
| tanδ(0℃) | 0.6026 | 0.4191 |
| tanδ(60℃) | 0.0665 | 0.0921 |
| Tan δ ratio (0 ℃/60 ℃) | 9.06 | 4.55 |
Embodiment 9
In 5 liters of stainless steel stirring tanks, add 3300 milliliters of hexanaphthenes, 87.5 gram vinylbenzene, 150 gram divinyl, 112.5 gram isoprene, 17 milliliters of tetrahydrofuran solutions, and at 55 ℃ of 5 milliliters of stanniferous single lithium compound initiators (solvent is a hexanaphthene) that add embodiment 1 preparation down, reacted 75 minutes, the system top temperature reaches 80 ℃.Add 10 milliliters of SiCl then
4Solution continues reaction, adds 6 milliliters of aqueous isopropanol terminators in 105 minutes.Add anti-aging agent Irganox1520 in the glue that obtains, add-on is 0.2 weight % of dried glue, with hot water cohesion, hot-rolling drying treatment.Sample is carried out the physicals test, and the result is as shown in table 5 below.
The microtexture that obtains this synthetic terpolymer rubber by above-mentioned determination of infrared spectroscopy is: 1, and 2-Bd% (mass ratio) 14.91%, 1,4-Bd% (mass ratio) is 27.94%, 1, and 4-Ip% (mass ratio) is 18.68%, 3,4-Ip% (mass ratio) is 13.47%.
Table 5
| Project | Embodiment 9 | Comparative Examples 4 |
| M Peak value(×10 5) | 17.3 | 16.7 |
| Coupling (%) | 57 | 55 |
| Shao Er hardness | 66 | 66 |
| Tear strength (MPa) | 38 | 37 |
| Tension set (%) | 8 | 8 |
| Mooney viscosity | 63 | 62 |
| 300% tensile modulus (MPa) | 13.2 | 10.4 |
| Tensile strength at yield (MPa) | 23.6 | 19.9 |
| Specific elongation (%) | 449 | 489 |
| Tg(℃) | -36.6 | -43.4 |
| tanδ(0℃) | 0.6781 | 0.4039 |
| tanδ(60℃) | 0.0658 | 0.0916 |
| Tan δ ratio (0 ℃/60 ℃) | 10.31 | 4.41 |
Embodiment 10
In 5 liters of stainless steel stirring tanks, add 3300 milliliters of hexanaphthenes, 70 gram vinylbenzene, 140 gram divinyl, 140 gram isoprene, 17 milliliters of tetrahydrofuran solutions, and at 55 ℃ of 8 milliliters of stanniferous single lithium compound initiators (solvent is a hexanaphthene) that add preparation among the embodiment 4 down, reacted 60 minutes, the system top temperature reaches 85 ℃.Add 5 milliliters of SnCl then
4Solution continues reaction, added 10 milliliters of tributyl tin chlorine solution and carry out end-blocking in 90 minutes.In 120 minutes, add 6 milliliters of aqueous isopropanol terminators then.Add anti-aging agent Irganox1520 in the glue that obtains, add-on is 0.2 weight of dried glue, with hot water cohesion, hot-rolling drying treatment.Sample is carried out the physicals test, and the result is as shown in table 6 below.
The microtexture that obtains this synthetic terpolymer rubber by above-mentioned determination of infrared spectroscopy is: 1, and 2-Bd% (mass ratio) 13.8%, 1,4-Bd% (mass ratio) is 26.2%, 1, and 4-Ip% (mass ratio) is 23.36%, 3,4-Ip% (mass ratio) is 16.64%.
Table 6
| Project | Embodiment 6 | Embodiment 10 * |
| M Peak value(×10 5) | 17.6 | 17.2 |
| Coupling (%) | 47.0 | 48.0 |
| Shao Er hardness | 64 | 66 |
| Tear strength (MPa) | 39 | 37 |
| Tension set (%) | 5 | 7 |
| Mooney viscosity | 83 | 79 |
| 300% tensile modulus (MPa) | 11.9 | 12.4 |
| Tensile strength at yield (MPa) | 21.8 | 22.1 |
| Specific elongation (%) | 456 | 469 |
| Tg(℃) | -40 | -38.9 |
| tanδ(0℃) | 0.5238 | 0.5319 |
| tanδ(60℃) | 0.0704 | 0.0651 |
| Tan δ ratio (0 ℃/60 ℃) | 7.44 | 8.17 |
*: be to have adopted 10 milliliters of tributyl tin chlorine solution further to carry out termination process with the difference of embodiment 6.
Embodiment 11
In 5 liters of stainless steel stirring tanks, add 3300 milliliters of hexanaphthenes, 80 gram vinylbenzene, 130 gram divinyl, 140 gram isoprene, 17 milliliters of tetrahydrofuran solutions, and at 55 ℃ of 25 milliliters of stanniferous single lithium compound initiators (solvent is a hexanaphthene) that add preparation among the embodiment 5, reacted 75 minutes, the system top temperature reaches 80 ℃.Add 10 milliliters of SiCl then
4Solution continues reaction, adds 6 milliliters of aqueous isopropanol terminators in 105 minutes.Add anti-aging agent Irganox1520 in the glue that obtains, add-on is 0.2 weight % of dried glue, with hot water cohesion, hot-rolling drying treatment.Sample is carried out the physicals test, and the result is as shown in table 7 below.
The microtexture that obtains this synthetic terpolymer rubber by above-mentioned determination of infrared spectroscopy is: 1, and 2-Bd% (mass ratio) 12.93%, 1,4-Bd% (mass ratio) is 24.22%, 1, and 4-Ip% (mass ratio) is 23.24%, 3,4-Ip% (mass ratio) is 16.76%.
Table 7
| Project | Embodiment 11 | Comparative Examples 5 |
| M Peak value(×10 5) | 18.0 | 17.7 |
| Coupling (%) | 56.2 | 57.0 |
| Shore hardness | 67 | 66 |
| Tear strength (MPa) | 38 | 38 |
| Tension set (%) | 9 | 8 |
| Mooney viscosity | 65 | 63 |
| 300% tensile modulus (MPa) | 13.4 | 10.5 |
| Tensile strength at yield (MPa) | 23.7 | 19.8 |
| Specific elongation (%) | 459 | 485 |
| Tg(℃) | -35.6 | -42.9 |
| tanδ(0℃) | 0.6801 | 0.4121 |
| tanδ(60℃) | 0.0683 | 0.0908 |
| Tan δ ratio (0 ℃/60 ℃) | 9.96 | 4.53 |
By the data during as above each is shown as seen, with Comparative Examples and rubber phase ratio commonly used, adopt the terpolymer rubber of the inventive method preparation to have extremely low rolling resistance performance and good wet-sliding resistant performance, its tan δ value of 60 ℃ is below 0.071,0 ℃ tan δ value is more than 0.523, and wherein the ratio of the tan δ value of 0 ℃ tan δ value and 60 ℃ is more than 7.Simultaneously, shown in embodiment 10, adopt at the end of link coupled polymkeric substance not to contain tin reagent and carry out end-blocking, further introduced tin atom, can further reduce the rolling resistance of copolymer rubber.
Claims (29)
1. the preparation method of a terpolymer, the head end of each bar polymer segment of this terpolymer all contains a tin atom, described method is included in and adopts stanniferous single lithium compound in the inert gas environment is initiator, in one or more varsols in the presence of polar additive, conjugated diene 1/ conjugated diene 2/ mono vinyl arenes monomer is carried out random copolymerization, after polymerization is finished, add terminator and stop living polymer chains;
Wherein said stanniferous single lithium compound is for having the compound of following general formula (1):
R
3SnY
aZY
bLi (1)
Wherein: R is C
1-C
20Alkyl, C
3-C
20Cycloalkyl or C
6-C
20Aryl or substituted aryl; Z is straight chain or branched C
1-C
20Bivalent hydrocarbon radical, C
6-C
30Arylidene or replacement arylidene; Y is a conjugated diolefine homopolymerization group, monovinylarene homopolymerization group or conjugated diolefine and monovinylarene copolymerization group; A is 0-6, does not comprise end points 6; 0≤a+b≤6, and during b=0, a must equal 0.
2. according to the process of claim 1 wherein that described conjugated diene 1 and conjugated diene 2 are different and being C
4-C
6Conjugated diene monomer.
3. according to the method for claim 2, wherein said conjugated diene 1 and conjugated diene 2 are selected from divinyl, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethylbutadiene and composition thereof.
4. according to the method for claim 3, wherein said conjugated diene 1 and conjugated diene 2 are selected from divinyl and isoprene.
5. according to the process of claim 1 wherein that described mono vinyl arenes monomer is selected from the vinylbenzene of vinylbenzene or alkyl replacement.
6. according to the method for claim 5, wherein said mono vinyl arenes monomer is selected from vinylbenzene, Vinyl toluene, alpha-methyl styrene, 4-t-butyl styrene, 4-vinyl toluene, 3,5-diethylbenzene ethene, 3,5-di-n-butyl vinylbenzene, 4-n-propylbenzene ethene, 4-dodecyl vinylbenzene and composition thereof.
7. according to the method for claim 6, wherein said mono vinyl arenes monomer is selected from vinylbenzene, Vinyl toluene, alpha-methyl styrene and composition thereof.
8. according to the method for claim 7, wherein said mono vinyl arenes monomer is a vinylbenzene.
9. according to each method among the claim 1-8, wherein said varsol is selected from naphthenic hydrocarbon, aromatic hydrocarbons, isoparaffin or its mixture that contains 5-7 carbon atom.
10. according to the method for claim 9, wherein said varsol is selected from benzene, toluene, hexane, hexanaphthene, pentane, heptane, hexane/hexanaphthene mixture.
11. according to each method among the claim 1-8, wherein said polar additive is selected from ether, dibutyl ether, tetrahydrofuran (THF), glycol dimethyl ether, diglyme, dioxane, crown ether, triethylamine, Tetramethyl Ethylene Diamine, HMPA, potassium tert.-butoxide, tertiary amyl alcohol potassium, potassium lauryl, alkyl benzene sulphonate (ABS) potassium, sodium alkyl benzene sulfonate and composition thereof.
12. according to each method among the claim 1-8, the mol ratio of wherein said polar additive and stanniferous single lithium compound is 0.1 to 200.
13. according to the method for claim 12, the mol ratio of wherein said polar additive and stanniferous single lithium compound is 1.0 to 100.
14. according to each method among the claim 1-8, wherein said terminator is water or alcohols terminator.
15. according to each method among the claim 1-8, it further is included in after polyreaction finishes, add before the terminator, in reaction system, add the coupling agent that is selected from many vinyl aromatic (co)s hydro carbons, polyfunctional epoxies, imines class, aldehydes, ketone, acid anhydride class, ester class, isocyanates and polyhalogenide.
16. according to the method for claim 15, it further is included in after the coupling, adds end-capping reagent link coupled segment is not carried out termination process.
17. according to the method for claim 16, the mol ratio of the same not coupling part of wherein said end-capping reagent is 0.2-1.0.
18. according to the method for claim 17, the mol ratio of the same not coupling part of wherein said end-capping reagent is 0.5-1.0.
19. terpolymer by conjugated diene 1/ conjugated diene 2/ monovinylarene of each method preparation among the claim 1-18.
20. according to the terpolymer of claim 19, the number-average molecular weight of wherein said terpolymer is 1.0 * 10
5-5.0 * 10
5, molecular weight distribution is 1.1-2.5.
21. according to the terpolymer of claim 20, the number-average molecular weight of wherein said terpolymer is 1.2 * 10
5-2.5 * 10
5, molecular weight distribution is 1.1-2.5.
22. according to the terpolymer of claim 19, the coupling efficiency of wherein said terpolymer is 20-100%.
23. according to the terpolymer of claim 22, the coupling efficiency of wherein said terpolymer is 30-80%.
24. terpolymer according to claim 19, wherein the gross weight in terpolymer is a benchmark, the content of described mono vinyl arenes monomer is 10-40 weight %, and conjugated diene 1 monomeric content is that 5-85 weight % and conjugated diene 2 monomeric content are 5-85 weight %.
25. terpolymer according to claim 24, wherein the gross weight in terpolymer is a benchmark, the content of described mono vinyl arenes monomer is 15-25 weight %, and conjugated diene 1 monomeric content is that 20-60 weight % and conjugated diene 2 monomeric content are 20-60 weight %.
26. according to the terpolymer of claim 19, wherein said terpolymer in the time of 0 ℃ tan δ value and the ratio of the tan δ value 60 ℃ the time more than 7.
27. according to each terpolymer among the claim 19-26, wherein said mono vinyl arenes monomer is a vinylbenzene, conjugated diene 1 monomer is a divinyl, and conjugated diene 2 monomers are isoprene.
28. according to the terpolymer of claim 27, the 1 structural content is 10-30 weight % in the wherein said terpolymer, 3, and 4-isoprene structural content is 10-30 weight %.
29. the application of each terpolymer in the preparation tire product among the claim 19-28.
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| CN102344529B (en) * | 2010-08-05 | 2013-10-16 | 中国石油天然气股份有限公司 | Preparation method of star-shaped solution polymerized styrene-butadiene rubber with wide molecular weight distribution |
| CN102372823B (en) * | 2010-08-26 | 2012-12-19 | 中国石油化工股份有限公司 | Terpolymer rubber with medium/high side group content and preparation method and applications thereof |
| CN103087261B (en) * | 2011-10-28 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of terpolymer and preparation method thereof and synthetic rubber and application |
| CN104558412B (en) * | 2013-10-17 | 2017-04-26 | 中国石油化工股份有限公司 | Monovinyl arene-conjugated diene copolymer composition as well as preparation method and application thereof |
| TWI506043B (en) * | 2013-12-31 | 2015-11-01 | Chi Mei Corp | Copolymer of isoprene and vinyl aromatic hydrocarbon and the synthesis method thereof |
| CN106188163B (en) * | 2015-04-30 | 2019-01-25 | 中国石油化工股份有限公司 | Trialkyl or triaryl tinbase lithium alkylide and its preparation method and application |
| CN106256843B (en) * | 2015-06-19 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of olefin copolymer and its preparation method and application |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5268439A (en) * | 1991-01-02 | 1993-12-07 | Bridgestone/Firestone, Inc. | Tin containing elastomers and products having reduced hysteresis properties |
| US5502129A (en) * | 1994-05-13 | 1996-03-26 | Bridgestone Corporation | Triorganotin lithium, process to prepare same and anionic polymerization initiated therewith |
| US5798408A (en) * | 1997-03-05 | 1998-08-25 | The Goodyear Tire & Rubber Company | Tire tread of coupled SIBR |
| US5877336A (en) * | 1996-12-31 | 1999-03-02 | Bridgestone Corporation | Synthesis of tributyltin lithium |
| CN1263116A (en) * | 2000-02-17 | 2000-08-16 | 北京燕山石油化工公司研究院 | Butadiene-styrene triblock copolymer and its preparation method |
| CN1350012A (en) * | 2000-10-19 | 2002-05-22 | 中国石油化工股份有限公司 | Star-shaped butadiene, isopene and styrene block copolymer and its prepn |
| CN1429849A (en) * | 2001-12-31 | 2003-07-16 | 中国石油化工股份有限公司 | Organic lithium compound containing tin and its preparation method |
| CN1495208A (en) * | 2002-06-13 | 2004-05-12 | 北京燕山石油化工公司研究院 | Method for preparing conjugated diolefine/monovinyl aromatic hydrocarbon copolymer rubber by means of solution polymeriaztion |
-
2007
- 2007-02-28 CN CN2007100641123A patent/CN101255223B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5268439A (en) * | 1991-01-02 | 1993-12-07 | Bridgestone/Firestone, Inc. | Tin containing elastomers and products having reduced hysteresis properties |
| US5502129A (en) * | 1994-05-13 | 1996-03-26 | Bridgestone Corporation | Triorganotin lithium, process to prepare same and anionic polymerization initiated therewith |
| US5877336A (en) * | 1996-12-31 | 1999-03-02 | Bridgestone Corporation | Synthesis of tributyltin lithium |
| US5798408A (en) * | 1997-03-05 | 1998-08-25 | The Goodyear Tire & Rubber Company | Tire tread of coupled SIBR |
| CN1263116A (en) * | 2000-02-17 | 2000-08-16 | 北京燕山石油化工公司研究院 | Butadiene-styrene triblock copolymer and its preparation method |
| CN1350012A (en) * | 2000-10-19 | 2002-05-22 | 中国石油化工股份有限公司 | Star-shaped butadiene, isopene and styrene block copolymer and its prepn |
| CN1429849A (en) * | 2001-12-31 | 2003-07-16 | 中国石油化工股份有限公司 | Organic lithium compound containing tin and its preparation method |
| CN1495208A (en) * | 2002-06-13 | 2004-05-12 | 北京燕山石油化工公司研究院 | Method for preparing conjugated diolefine/monovinyl aromatic hydrocarbon copolymer rubber by means of solution polymeriaztion |
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